UV waterproof ink and preparation method thereof

Abstract

The invention discloses UV waterproof ink and a preparation method thereof, and relates to the technical field of UV waterproof ink. An esterification product of linoleic acid and linoleyl alcohol is used as an A-phase component of the ink, mercapto-terminated polyethylene glycol is used as a B-phase component of the ink, the film-forming speed of the ink under the action of ultraviolet light is increased by utilizing a thiol-ene click reaction, and a polyethylene glycol skeleton introduced into the structure has a good film-forming effect. In the ultraviolet curing process, the photoinitiator is connected into a three-dimensional network formed after the ink is cured, the viscosity of the ink is improved, the binding force between the ink and a printing medium is improved, rosmarinic acid and mercaptoethylamine are used for forming a self-made antioxidant under ultraviolet irradiation, the self-made antioxidant is added into the ink, oxygen is efficiently captured, other components in the ink are protected, and the ink has the advantages of being environmentally friendly and free of toxic and side effects. The service life of ink is prolonged. The prepared UV waterproof ink is high in ultraviolet curing rate, waterproof, temperature-resistant and high in oxidation resistance.

Description

Technical Field

[0001] The invention relates to the technical field of UV waterproof ink, in particular to a UV waterproof ink and a preparation method thereof. Background Art

[0002] With the continuous advancement of printing technology and the rapid development of the printing industry, the performance requirements for printing inks are also constantly increasing. Traditional inks have certain limitations in terms of drying speed, anti-oxidation and aging, adhesion, etc. At the same time, during the production and use process, they may produce harmful substances such as volatile organic compounds (VOCs), which pollute the environment. Especially in the printing field that requires fast drying and waterproof effects, for example, in advertising, decoration, 3C products, signs and signs, imitation paintings, industry and other fields, traditional inks often cannot meet the requirements. With the growing market demand for high-quality printed products and the continuous innovation of technology, the research and development and application of UV waterproof inks have also developed rapidly. With the development of new monomers, resins and additives, as well as the continuous improvement of photoinitiators, the performance of UV waterproof inks is also constantly improving, the scope of application is also constantly expanding, and people are paying more and more attention to the environmental performance of printing inks. UV waterproof inks use ultraviolet curing technology, and there is no VOCs emission during the curing process, which meets environmental protection requirements, so they are favored by the government and enterprises. Therefore, the development of new inks with characteristics such as fast curing, waterproofing, and anti-oxidation has become an important demand of the printing industry. Summary of the invention

[0003] The purpose of the present invention is to provide a UV waterproof ink to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: a UV waterproof ink, the UV waterproof ink comprising a phase A component and a phase B component, wherein the phase A component comprises a linoleic acid linoleyl ester compound, a pigment, a mercapto polysiloxane, and a homemade antioxidant, and the phase B component comprises a terminal mercapto polyethylene glycol, a photoinitiator, glycerol, trimethyl aluminum, and a homemade antioxidant.

[0005] Furthermore, the homemade antioxidant is prepared by reacting rosmarinic acid and mercaptoethylamine with a photoinitiator under ultraviolet light.

[0006] Furthermore, the pigment is one or more of carbon black, red iron oxide, yellow iron oxide, phthalocyanine blue, phthalocyanine green, scarlet, sun-fast yellow, and permanent violet; the molecular weight of mercapto polysiloxane is 400-800, and the molecular weight of terminal mercapto polyethylene glycol is 2000-3000.

[0007] Furthermore, the photoinitiator is one or more of benzophenone, thioxanthone, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2,2-dimethoxy-2-phenylacetophenone.

[0008] Furthermore, a method for preparing a UV waterproof ink comprises the following preparation steps:

[0009] (1) taking rosmarinic acid, mercaptoethylamine, and a photoinitiator and dissolving them in anhydrous ethanol, stirring them for 2 to 4 hours at 40 to 60° C., a UV wavelength of 250 to 360 nm, and a stirring rate of 200 to 400 r / min under a nitrogen atmosphere, and then transferring them to a drying oven and drying them at 50 to 60° C. for 2 to 4 hours to obtain a homemade antioxidant;

[0010] (2) adding linoleic acid, linoleyl alcohol and 60% sulfuric acid to anhydrous ethanol, placing in an oil bath at 40-50°C, stirring at a speed of 300-600 r / min for 4-8 hours under a nitrogen atmosphere, cooling to room temperature, and then performing rotary evaporation to remove the solvent to obtain a crude product, re-dissolving the crude product in tetrahydrofuran to prepare a solution C in which the crude product accounts for 50-60 wt%, and then adding the solution C to n-hexane at a speed of 0.5-1 drop / s, with a volume ratio of n-hexane to solution C of 3:1, standing for 10-18 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally obtaining crystals, then pouring off the upper solvent, draining with a vacuum pump, and then dissolving with tetrahydrofuran, repeating the crystallization 5-8 times, and finally obtaining an alcohol ester compound;

[0011] (3) adding the alcohol ester compound, the pigment, the mercapto polysiloxane, and the homemade antioxidant to anhydrous ethanol, stirring at 50 to 80° C. and a stirring rate of 100 to 300 r / min for 3 to 6 hours to obtain an ink phase A component;

[0012] (4) Add terminal mercapto polyethylene glycol, photoinitiator, propylene glycol, trimethyl aluminum, and homemade antioxidant to anhydrous ethanol, stir at 50-80° C. and a stirring rate of 100-300 r / min for 3-6 hours to obtain ink phase B component.

[0013] Furthermore, in step (1), by weight, 30 to 60 parts of rosmarinic acid, 20 to 40 parts of mercaptoethylamine, 1 to 5 parts of photoinitiator, and 50 to 60 parts of anhydrous ethanol are included.

[0014] Furthermore, in step (2), by weight, 20 to 30 parts of linoleic acid, 15 to 25 parts of linoleyl alcohol, 20 to 30 parts of sulfuric acid, and 50 to 60 parts of anhydrous ethanol are used.

[0015] Furthermore, in step (3), by weight, 30 to 40 parts of alcohol ester compound, 10 to 20 parts of pigment, 5 to 10 parts of mercapto polysiloxane, 20 to 30 parts of homemade antioxidant, and 50 to 60 parts of anhydrous ethanol are used.

[0016] Furthermore, in step (4), by weight, 25 to 45 parts of terminal mercapto polyethylene glycol, 2 to 8 parts of photoinitiator, 10 to 20 parts of propylene glycol, 1 to 5 parts of trimethylaluminum, 20 to 30 parts of homemade antioxidant, and 50 to 60 parts of anhydrous ethanol are used.

[0017] Furthermore, when the ink is used, 50 parts of ink phase A and 50 parts of ink phase B are mixed and stirred evenly. After printing, the ink is cured for 0.5 to 2 seconds under ultraviolet light wavelength of 350 to 400 nm.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] The UV waterproof ink prepared by the invention improves the waterproof, heat-resistant and anti-oxidation properties of the ink on the basis of realizing ultraviolet high-speed curing.

[0020] Firstly, the esterification product of linoleic acid and linoleyl alcohol is used as the A phase component of the ink to introduce more double bonds into the ink, provide sufficient double bond functional groups for the thiol-ene polymerization reaction during the ink curing process, increase the concentration of the double bond functional groups in the system, accelerate the ultraviolet curing rate of the ink, and introduce a large number of alkyl groups into the ink, so that the cured ink has high hydrophobicity, and blocks the passage of water molecules into the ink in advance after film formation, which effectively plays a waterproof role. At the same time, terminal thiol polyethylene glycol is used as the B phase component of the ink to provide double thiol groups for the thiol-ene polymerization reaction during the ultraviolet curing of the ink, so as to achieve efficient light curing performance of the ink. The polyethylene glycol skeleton introduced into the structure is connected to the three-dimensional network formed after the ink is cured during the ultraviolet curing process, which effectively improves the viscosity of the ink, improves the bonding force between the ink and the printing medium, makes the printed product clearer and the color more saturated, and the ether bonds in the polyethylene glycol skeleton have high thermal stability, which further improves the high temperature resistance of the ink.

[0021] Secondly, rosmarinic acid and mercaptoethylamine are reacted under ultraviolet light to introduce amino groups into rosmarinic acid to form a homemade antioxidant, which is then added to the ink. When oxygen in the air attacks the ink, the phenolic hydroxyl and amino groups in the antioxidant structure can efficiently capture oxygen to form stable compounds, thereby protecting other components in the ink from oxygen erosion and extending the life of the ink. The benzene ring in the structure provides a stable structure for the antioxidant, extending the service life of the oxidant. The carboxyl group in the structure can react with the functional groups of the printing medium during the curing process of the ink, so that the antioxidant is bonded to the printing medium through chemical bonds, thereby enhancing the adhesion ability of the antioxidant and allowing the cured ink to continue to maintain high-efficiency antioxidant properties. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0023] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the UV waterproof ink prepared in the following examples.

[0024] Ink viscosity: According to GB / T 13217.4-2008, the viscosity of the UV waterproof ink prepared in Examples 1-3 and Comparative Examples 1-5 was tested;

[0025] Curing time: quantitatively roll coating on the substrate, irradiation with ultraviolet light at a wavelength of 380 nm, and dry method to characterize complete curing, and test the curing time of the UV waterproof ink prepared in Examples 1-3 and Comparative Examples 1-5;

[0026] Ink flexibility: Referring to GB / T1731.93, the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 were tested using a QTX.1 paint film elasticity tester to determine the flexibility of the coating film;

[0027] Smear pencil hardness: Referring to GB6739.86, the pencil hardness of the coating film was determined by using a QHQ coating pencil scratch hardness tester to test the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5;

[0028] Ink adhesion: Referring to GB9256-88, the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 were tested by a cross-cut test to determine the adhesion of the coating film;

[0029] Waterproof property: quantitatively roll-coat the film base, irradiate with ultraviolet light of 380 nm, and after curing into a film, soak in 40° C. warm water for 240 h, and observe the appearance changes of the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5.

[0030] Example 1

[0031] (1) 30 parts of rosmarinic acid, 20 parts of mercaptoethylamine, and 1 part of benzophenone were dissolved in 50 parts of anhydrous ethanol, stirred at 50° C., ultraviolet light wavelength of 320 nm, and a stirring rate of 350 r / min for 4 h under a nitrogen atmosphere, and then moved to a drying oven and dried at 50° C. for 3 h to obtain a homemade antioxidant;

[0032] (2) 20 parts of linoleic acid, 15 parts of linoleyl alcohol, and 20 parts of 60% sulfuric acid are added to 50 parts of anhydrous ethanol, and stirred at a speed of 400 r / min for 6 hours in an oil bath at 50°C and a nitrogen atmosphere, and then cooled to room temperature, and then the solvent is removed by rotary evaporation to obtain a crude product, and the crude product is redissolved in tetrahydrofuran to prepare a solution C in which the crude product accounts for 60wt%, and then the solution C is added to n-hexane at a speed of 1 drop / s, and the volume ratio of n-hexane to solution C is 3:1, and the solution is allowed to stand for 15 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally crystals are obtained, and then the upper solvent is poured off, and the solution is dried with a vacuum pump, and then dissolved with tetrahydrofuran, and the crystallization is repeated 6 times to finally obtain an alcohol ester compound;

[0033] (3) adding 30 parts of alcohol ester compound, 10 parts of pigment, 5 parts of mercapto polysiloxane with a molecular weight of 600, and 20 parts of homemade antioxidant to 50 parts of anhydrous ethanol, stirring at 60° C. and a stirring rate of 200 r / min for 5 h to obtain ink phase A component;

[0034] (4) Add 25 parts of 2000 molecular weight end-mercapto polyethylene glycol, 2 parts of benzophenone, 10 parts of propylene glycol, 1 part of trimethylaluminum, and 20 parts of homemade antioxidant to 50-60 parts of anhydrous ethanol, stir at 60°C and a stirring rate of 250 r / min for 6 hours to obtain the ink phase B component.

[0035] Example 2

[0036] (1) 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine, and 3 parts of benzophenone were dissolved in 55 parts of anhydrous ethanol, stirred at 50° C., ultraviolet light wavelength of 320 nm, and a stirring rate of 350 r / min for 4 h under a nitrogen atmosphere, and then moved to a drying oven and dried at 50° C. for 3 h to obtain a homemade antioxidant;

[0037] (2) 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of 60% sulfuric acid were added to 55 parts of anhydrous ethanol, and stirred at a speed of 400 r / min for 6 hours in an oil bath at 50°C and a nitrogen atmosphere, and then cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a crude product, and the crude product was redissolved in tetrahydrofuran to prepare a solution C in which the crude product accounted for 60wt%. Then, the solution C was added to n-hexane at a rate of 1 drop / s, and the volume ratio of n-hexane to solution C was 3:1. The solution was allowed to stand for 15 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to finally obtain crystals, and then the upper solvent was poured off, the solution was dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization was repeated 6 times to finally obtain an alcohol ester compound;

[0038] (3) adding 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercapto polysiloxane with a molecular weight of 600, and 25 parts of homemade antioxidant to 55 parts of anhydrous ethanol, stirring at 60° C. and a stirring rate of 200 r / min for 5 h to obtain ink phase A component;

[0039] (4) 35 parts of 2000 molecular weight end-mercapto polyethylene glycol, 5 parts of benzophenone, 15 parts of propylene glycol, 3 parts of trimethylaluminum, and 25 parts of homemade antioxidant were added to 55 parts of anhydrous ethanol, and stirred at 60° C. and a stirring rate of 250 r / min for 6 h to obtain the ink phase B component.

[0040] Example 3

[0041] (1) 60 parts of rosmarinic acid, 40 parts of mercaptoethylamine, and 5 parts of benzophenone were dissolved in 60 parts of anhydrous ethanol, stirred at 50° C., ultraviolet light wavelength of 320 nm, and stirring rate of 350 r / min for 4 h under nitrogen atmosphere, and then moved to a drying oven and dried at 50° C. for 3 h to obtain a homemade antioxidant;

[0042] (2) 30 parts of linoleic acid, 25 parts of linoleyl alcohol, and 30 parts of 60% sulfuric acid by mass were added to 60 parts of anhydrous ethanol, and stirred at a speed of 400 r / min for 6 hours in an oil bath at 50°C and a nitrogen atmosphere, and then cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a crude product, and the crude product was redissolved in tetrahydrofuran to prepare a solution C in which the crude product accounted for 60wt%. Then, the solution C was added to n-hexane at a speed of 1 drop / s, and the volume ratio of n-hexane to solution C was 3:1. The solution was allowed to stand for 15 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to obtain crystals, and then the upper solvent was poured off, the solution was dried with a vacuum pump, and then dissolved in tetrahydrofuran. The crystallization was repeated 6 times to finally obtain an alcohol ester compound;

[0043] (3) adding 40 parts of alcohol ester compound, 20 parts of pigment, 10 parts of mercapto polysiloxane with a molecular weight of 600, and 30 parts of homemade antioxidant to 60 parts of anhydrous ethanol, stirring at 60° C. and a stirring rate of 200 r / min for 5 h to obtain ink phase A component;

[0044] (4) 45 parts of 2000 molecular weight end-mercapto polyethylene glycol, 8 parts of benzophenone, 20 parts of propylene glycol, 5 parts of trimethylaluminum, and 30 parts of a homemade antioxidant were added to 60 parts of anhydrous ethanol, and stirred at 60° C. and a stirring rate of 250 r / min for 6 h to obtain the ink phase B component.

[0045] Comparative Example 1

[0046] (1) 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of 60% sulfuric acid are added to 55 parts of anhydrous ethanol, and stirred at a speed of 400 r / min for 6 hours in an oil bath at 50°C and a nitrogen atmosphere, and then cooled to room temperature, and then the solvent is removed by rotary evaporation to obtain a crude product, and the crude product is redissolved in tetrahydrofuran to prepare a solution C in which the crude product accounts for 60wt%, and then the solution C is added to n-hexane at a speed of 1 drop / s, and the volume ratio of n-hexane to solution C is 3:1, and the solution is allowed to stand for 15 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally crystals are obtained, and then the upper solvent is poured off, and the solution is dried with a vacuum pump, and then dissolved with tetrahydrofuran, and the crystallization is repeated 6 times to finally obtain an alcohol ester compound;

[0047] (2) adding 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600, and 25 parts of mercaptoethylamine to 55 parts of anhydrous ethanol, stirring at 60° C. and a stirring rate of 200 r / min for 5 h to obtain ink phase A component;

[0048] (3) Add 35 parts of 2000 molecular weight terminated mercapto polyethylene glycol, 5 parts of benzophenone, 15 parts of propylene glycol, 3 parts of trimethylaluminum, and 25 parts of mercaptoethylamine to 55 parts of anhydrous ethanol, and stir at 60°C and a stirring rate of 250 r / min for 6 h to obtain the ink phase B component.

[0049] Comparative Example 2

[0050] (1) 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of 60% sulfuric acid are added to 55 parts of anhydrous ethanol, and stirred at a speed of 400 r / min for 6 hours in an oil bath at 50°C and a nitrogen atmosphere, and then cooled to room temperature, and then the solvent is removed by rotary evaporation to obtain a crude product, and the crude product is redissolved in tetrahydrofuran to prepare a solution C in which the crude product accounts for 60wt%, and then the solution C is added to n-hexane at a speed of 1 drop / s, and the volume ratio of n-hexane to solution C is 3:1, and the solution is allowed to stand for 15 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally crystals are obtained, and then the upper solvent is poured off, and the solution is dried with a vacuum pump, and then dissolved with tetrahydrofuran, and the crystallization is repeated 6 times to finally obtain an alcohol ester compound;

[0051] (2) adding 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercapto polysiloxane with a molecular weight of 600, and 25 parts of rosmarinic acid to 55 parts of anhydrous ethanol, stirring at 60° C. and a stirring rate of 200 r / min for 5 h to obtain ink phase A component;

[0052] (3) Add 35 parts of 2000 molecular weight end-mercapto polyethylene glycol, 5 parts of benzophenone, 15 parts of propylene glycol, 3 parts of trimethylaluminum, and 25 parts of rosmarinic acid to 55 parts of anhydrous ethanol, and stir at 60° C. and a stirring rate of 250 r / min for 6 h to obtain the ink phase B component.

[0053] Comparative Example 3

[0054] (1) 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine, and 3 parts of benzophenone were dissolved in 55 parts of anhydrous ethanol, stirred at 50° C., ultraviolet light wavelength of 320 nm, and a stirring rate of 350 r / min for 4 h under a nitrogen atmosphere, and then moved to a drying oven and dried at 50° C. for 3 h to obtain a homemade antioxidant;

[0055] (2) adding 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600, and 25 parts of homemade antioxidant to 55 parts of anhydrous ethanol, stirring at 60° C. and a stirring rate of 200 r / min for 5 h to obtain ink phase A component;

[0056] (3) 35 parts of 2000 molecular weight end-mercapto polyethylene glycol, 5 parts of benzophenone, 15 parts of propylene glycol, 3 parts of trimethylaluminum, and 25 parts of a homemade antioxidant were added to 55 parts of anhydrous ethanol, and stirred at 60° C. and a stirring rate of 250 r / min for 6 h to obtain the ink phase B component.

[0057] Comparative Example 4

[0058] (1) 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine, and 3 parts of benzophenone were dissolved in 55 parts of anhydrous ethanol, stirred at 50° C., ultraviolet light wavelength of 320 nm, and a stirring rate of 350 r / min for 4 h under a nitrogen atmosphere, and then moved to a drying oven and dried at 50° C. for 3 h to obtain a homemade antioxidant;

[0059] (2) 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of 60% sulfuric acid were added to 55 parts of anhydrous ethanol, and stirred at a speed of 400 r / min for 6 hours in an oil bath at 50°C and a nitrogen atmosphere, and then cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a crude product, and the crude product was redissolved in tetrahydrofuran to prepare a solution C in which the crude product accounted for 60wt%. Then, the solution C was added to n-hexane at a rate of 1 drop / s, and the volume ratio of n-hexane to solution C was 3:1. The solution was allowed to stand for 15 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to finally obtain crystals, and then the upper solvent was poured off, the solution was dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization was repeated 6 times to finally obtain an alcohol ester compound;

[0060] (3) adding 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercapto polysiloxane with a molecular weight of 600, and 25 parts of homemade antioxidant to 55 parts of anhydrous ethanol, stirring at 60° C. and a stirring rate of 200 r / min for 5 h to obtain ink phase A component;

[0061] (4) Add 5 parts of benzophenone, 15 parts of propylene glycol, 3 parts of trimethylaluminum, and 25 parts of a homemade antioxidant to 55 parts of anhydrous ethanol, and stir at 60° C. and a stirring rate of 250 r / min for 6 h to obtain the ink phase B component.

[0062] Comparative Example 5

[0063] (1) 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine, and 3 parts of benzophenone were dissolved in 55 parts of anhydrous ethanol, stirred at 50° C., ultraviolet light wavelength of 320 nm, and a stirring rate of 350 r / min for 4 h under a nitrogen atmosphere, and then moved to a drying oven and dried at 50° C. for 3 h to obtain a homemade antioxidant;

[0064] (2) 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of 60% sulfuric acid were added to 55 parts of anhydrous ethanol, and stirred at a speed of 400 r / min for 6 hours in an oil bath at 50°C and a nitrogen atmosphere, and then cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a crude product, and the crude product was redissolved in tetrahydrofuran to prepare a solution C in which the crude product accounted for 60wt%. Then, the solution C was added to n-hexane at a rate of 1 drop / s, and the volume ratio of n-hexane to solution C was 3:1. The solution was allowed to stand for 15 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran to finally obtain crystals, and then the upper solvent was poured off, the solution was dried with a vacuum pump, and then dissolved with tetrahydrofuran. The crystallization was repeated 6 times to finally obtain an alcohol ester compound;

[0065] (3) 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercapto polysiloxane with a molecular weight of 600, 50 parts of homemade antioxidant, 35 parts of terminal mercapto polyethylene glycol with a molecular weight of 2000, 5 parts of benzophenone, 15 parts of propylene glycol, and 3 parts of trimethylaluminum were added to 55 parts of anhydrous ethanol, and stirred at 60°C and a stirring rate of 200 r / min for 5 hours to obtain ink.

[0066] Effect example

[0067] Table 1 below shows the performance analysis results of the UV waterproof inks of Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0068] Table 1 Performance test results of UV waterproof ink prepared in Examples 1 to 3 and Comparative Examples 1 to 5

[0069]

[0070] From the results in Table 1, it can be seen that the UV waterproof ink prepared by the present invention has a fast curing rate and good adhesion. The cured ink exhibits excellent flexibility and high pencil hardness. After being soaked in water for 240 hours, it still maintains its original state and has high water resistance. By comparing the results of Example 2 with those of Comparative Example 5, it is found that when the two phases of the ink are mixed and stored, the quality of the ink will be affected. By comparing the results of Example 2 with those of Comparative Examples 3-4, it is found that the use of the alcohol ester compound improves the waterproof effect of the UV waterproof ink and improves the waterproof performance of the ink.

[0071] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A UV waterproof ink, characterized in that: The UV waterproof ink comprises a phase A component and a phase B component, wherein the phase A component comprises a linoleic acid linoleyl ester compound, a pigment, a mercapto polysiloxane, and a homemade antioxidant, and the phase B component comprises a terminal mercapto polyethylene glycol, a photoinitiator, glycerol, trimethyl aluminum, and a homemade antioxidant.

2. A UV waterproof ink according to claim 1, characterized in that: The self-made antioxidant is prepared by reacting rosmarinic acid and mercaptoethylamine with a photoinitiator under ultraviolet light irradiation.

3. A UV waterproof ink according to claim 1, characterized in that: The pigment is one or more of carbon black, red iron oxide, yellow iron oxide, phthalocyanine blue, phthalocyanine green, scarlet, sun-fast yellow and permanent violet; the molecular weight of mercapto polysiloxane is 400-800; the molecular weight of terminal mercapto polyethylene glycol is 2000-3000.

4. A UV waterproof ink according to any one of claims 1 or 2, characterized in that: The photoinitiator is one or more of benzophenone, thioxanthone, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2,2-dimethoxy-2-phenylacetophenone.

5. A method for preparing UV waterproof ink, characterized in that: The method comprises the following preparation steps: (1) taking rosmarinic acid, mercaptoethylamine, and a photoinitiator and dissolving them in anhydrous ethanol, stirring them for 2 to 4 hours at 40 to 60° C., a UV wavelength of 250 to 360 nm, and a stirring rate of 200 to 400 r / min under a nitrogen atmosphere, and then transferring them to a drying oven and drying them at 50 to 60° C. for 2 to 4 hours to obtain a homemade antioxidant; (2) adding linoleic acid, linoleyl alcohol and 60% sulfuric acid to anhydrous ethanol, placing in an oil bath at 40-50°C, stirring at a speed of 300-600 r / min for 4-8 hours under a nitrogen atmosphere, cooling to room temperature, and then performing rotary evaporation to remove the solvent to obtain a crude product, re-dissolving the crude product in tetrahydrofuran to prepare a solution C in which the crude product accounts for 50-60 wt%, and then adding the solution C to n-hexane at a speed of 0.5-1 drop / s, with a volume ratio of n-hexane to solution C of 3:1, standing for 10-18 hours to allow it to recrystallize at the interface of n-hexane and tetrahydrofuran, and finally obtaining crystals, then pouring off the upper solvent, draining with a vacuum pump, and then dissolving with tetrahydrofuran, repeating the crystallization 5-8 times, and finally obtaining an alcohol ester compound; (3) adding the alcohol ester compound, the pigment, the mercapto polysiloxane, and the homemade antioxidant to anhydrous ethanol, stirring at 50 to 80° C. and a stirring rate of 100 to 300 r / min for 3 to 6 hours to obtain an ink phase A component; (4) Add terminal mercapto polyethylene glycol, photoinitiator, propylene glycol, trimethyl aluminum, and homemade antioxidant to anhydrous ethanol, stir at 50-80° C. and a stirring rate of 100-300 r / min for 3-6 hours to obtain ink phase B component.

6. The method for preparing a UV waterproof ink according to claim 5, characterized in that: In step (1), by weight, 30 to 60 parts of rosmarinic acid, 20 to 40 parts of mercaptoethylamine, 1 to 5 parts of photoinitiator and 50 to 60 parts of anhydrous ethanol are included.

7. The method for preparing a UV waterproof ink according to claim 5, characterized in that: In step (2), the following are calculated by weight: 20-30 parts of linoleic acid, 15-25 parts of linoleyl alcohol, 20-30 parts of sulfuric acid, and 50-60 parts of anhydrous ethanol.

8. The method for preparing a UV waterproof ink according to claim 5, characterized in that: In step (3), the alcohol ester compound is 30 to 40 parts, the pigment is 10 to 20 parts, the mercapto polysiloxane is 5 to 10 parts, the homemade antioxidant is 20 to 30 parts, and the anhydrous ethanol is 50 to 60 parts, by weight.

9. The method for preparing a UV waterproof ink according to claim 5, characterized in that: In step (4), the following are calculated by weight: 25-45 parts of terminal mercapto polyethylene glycol, 2-8 parts of photoinitiator, 10-20 parts of propylene glycol, 1-5 parts of trimethylaluminum, 20-30 parts of homemade antioxidant, and 50-60 parts of anhydrous ethanol.

10. The method for preparing a UV waterproof ink according to claim 5, characterized in that: When the ink is used, 50 parts of ink phase A and 50 parts of ink phase B are mixed and stirred evenly. After printing, the ink is cured for 0.5 to 2 seconds under ultraviolet light with a wavelength of 350 to 400 nm.

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